1248564 玖、發明說明： 【發明所屬之技術領域】 本發明係關於一種在使用電子照相技術之複印機、印 刷機或傳真機等之影像形成裝置中所使用的電子照相用調 色劑、及使用彼等之影像形成方法。 【先前技術】 適用於使用電子照相技術之影像形成裝置之影像的乾 式顯像劑，大槪可分爲混合有由肥粒鐵粉、鐵粉、玻璃珠 等所形成的載體之雙成分系顯像劑的調色劑、調色劑本身 含有磁性粉末之磁性一成分系顯像劑、及非磁性一成分顯 像劑。可使用於此等之顯像劑的調色劑，係以黏合樹脂及 著色劑爲主成分，除此之外，爲了提昇記錄紙的低溫定像 性及定像組件之離型性的功能，以及爲了提昇極性（帶正電 或帶負電）也可添加帶電控制劑等。調色劑係將此等材料以 預定的摻混比例混合後’再經過溶解混練、粉碎、分級等 步驟而製造成粉末，最後爲了控制流動性、帶電性、新鮮 性及保存性等而再藉由矽石、氧化鈦、氧化鋁及各種之樹 脂微粒子之外添加劑來實施表面處理，再供給來做爲最終 的顯像劑。 就做爲調色劑之黏合樹脂者來說，係以苯乙烯-丙烯酸 酯系樹脂、及聚酯系樹脂爲主流。然而，在使用苯乙烯-丙 烯酸酯系樹脂做爲調色劑的情況下，雖然是耐環境特性良 好，但是破壞強度小以致會有容易產生微粉末之問題。又， 使用聚酯系樹脂的調色劑，雖然是破壞強度大而不易產生 6 1248564 微粉末，然而卻會有耐環境特性差的問題。 因而，現在所販賣的顯像劑，當然是一種顧慮了人體 及環境安全性且沒有實質上的問題之物質，然而近年來傾 向於選擇更顧慮人體及環境安全性之原材料，已成爲顯像 劑的特徵之一了。特別是，考量在調色劑中占大部分的黏 合樹脂之安全性、環境性以選擇其構成單體及殘留溶劑等， 已逐漸地成爲必要的事了。在像這樣的情況下，最近一直 受到囑目的調色劑用黏合樹脂，舉例來說有環烯烴共聚物 樹脂等，使用它之調色劑有在特開平9-101631公報、特開 2000-284528號公報皮特開2000-206732號公報上所揭示 者。此種樹脂之單體具有安全性，而且與苯乙烯-丙烯酸酯 系樹脂比較之下，由於真比重變小、體積固有電阻也變高 的緣故，所以顯像性及轉仙性（轉印效率）變優良，以及每 單位使用重量的印字數量大（調色劑之消牦量少）等之有利 點。更且，因爲樹脂之破壞強度大，所以可以達成顯像劑 之壽命加長化之有利點；又且由於光穿透性優良而也非常 適合於做爲全衫調色劑用之樹脂。 另一方面’將顯像劑定著於記錄媒體上之定像機，伴 隨著複印速度之高速化，加熱壓著方式已逐漸變成主流了。 此種方式，係爲一種使轉印紙通過與調色劑接觸側的定像 組件、和與調色劑非接觸之加壓輥之間，並同時施加熱和 壓力而將調色劑熔融定著於轉印紙上之方法。關於此種方 式，雖然定像組件多半是一組裝有熱源之輥，然而也可以 7 1248564 使用耐熱性薄膜等之帶。另一方面，調色劑非接觸側通常 是加壓輥。又，於調色劑定像之際，爲了防止熔融調色劑 附著在定像組件之表面上，則定像組件之表面材質宜選擇 一種對於苯乙烯-丙烯酸酯系樹脂及聚酯系樹脂之黏合樹脂 能顯示出剝離性之物質。特別是，對於和調色劑接觸之定 像組件更要求具有優異的剝離性。像這樣的剝離性物質中 之代表性物質「係有聚四氟乙烯（以下稱爲「P T F E」）及聚 矽氧橡膠。 惟，由於此等物質之耐熱性低，因而不能將定像組件 之表面溫度設定在高的狀態，或者要維持表面溫度亦是困 難的。因爲這樣的結果使得調色劑的定像速度不能提高， 則複印速度之昇高就受到限制了。 更且，含有環烯烴共聚物樹脂的黏合樹脂之調色劑， 使用於一般之加熱壓著式定像機之定像組件、及加壓輥之 表面上用的PTFE /聚矽氧、及聚矽氧/聚矽氧（影像表面/ 影像裡面）等之材質的組合予以定像之情況下，即使是添加 有如剝離劑之調色劑，難免影像面會從定像組件分離而捲 起，也就是發生所謂的捲曲現象。此種問題，雖然可藉由 減少環烯烴共聚物樹脂之低分子量成分的量而改善，然而， 由於此種方法對策同時地也損壞了低溫定像性，難謂是最 佳的良策，至目前爲止尙不能完全地解決捲曲現象。又， 此種樹脂，由於是與在苯乙烯·丙烯酸酯系樹脂、聚酯系等 之調色劑用黏合樹脂上所使用的聚丙烯、聚乙烯及天然蠟 8 1248564 等之剝離劑間的相溶性非地良好，因而與在剝離劑之定像 組件間也就會有不能確保充分的剝離性之問題。更且，因 爲此種樹脂具有強靭性，所以也會有定像組件表面容易磨 損的問題。 另一方面，近年來所販賣的複印機及印表機，由於爲 了能夠使維護變得簡便而有使消耗品個數最少化之傾向， 因而不能被使用者更換的組件就增加了，定像組件也是其 中之一者。此種組件有必要是經過長期間亦不會引起麻煩 者。但是，定像機是一種容易發生問題的物品，至今仍成 爲問題的時常發生捲曲等之情況，姑且不用說使用時煩雜， 光是必須要由專門業者來更換組件，在日常使用上即一直 是一種困擾。 【發明內容】 【發明之揭示】 從而，本發明之目的在於：提供一種電子照相用調色 劑及使用它之影像形成方法，其係一種當在用以環烯烴共 聚物做爲黏合樹脂使用之調色劑的情況下，即使是在多數 枚連續刷時也不發生定像時之偏位及捲曲現象，並可以維 持長期且充分之影像濃度等之良好顯像性；更且本發明之 目的亦在於：提供一種適合於全彩影像的電子照相用調色 劑及使用它之影像形成方法。 本發明之電子照相用調色劑，其係供於使用具備一具 有聚苯并咪唑含有表層的定像組件的加熱壓合式定像機之 9 1248564 影像形成方法中使用之調色劑，其特徵在於··含有至少一 種環烯烴共聚物樹脂之黏合樹脂。 又’本發明之電子照相用調色劑，其係含有環烯烴共 聚物樹脂之黏合樹脂，且該環烯烴共聚物樹脂係由〇〜7 5重 量％之重量平均分子量爲小於1 5000之低分子量體、5〜2 5 重量％之重量平均分子量爲15000〜100000之中分子量體、 及20〜95重量％之重量平均分子量爲超過100000之高分子 量體的混合物所構成。 又，本發明之影像形成方法，其特徵在於：將一具有 使用含有至少一種環烯烴共聚物樹脂之黏合樹脂的電子照 相用調色劑所形成的調色劑影像之轉印紙，供給到具備一 具有聚苯并咪唑含有表層的定像組件的加熱壓合式定像 機，再將該調色劑影像予以定像。 更且又，本發明之一種影像形成方法，其特徵在於：將 一具有使用含有至少一種環烯烴共聚物樹脂之黏合樹脂的 電子照相用調色劑所形成的調色劑影像之轉印紙，供給到 具備一具有聚苯并咪唑含有表層的定像組件的加熱壓合式 定像機，再將該調色劑影像予以定像；而且該環烯烴共聚 物樹脂係由〇〜7 5重量。/。之重量平均分子量爲小於1 5 0 0 0之 低分子量體、5〜25 重量％之重量平均分子量爲 15000〜100000之中分子量體、及20〜95重量。/。之重量平均 分子量爲超過100000之高分子量體的混合物所構成。 在本發明之影像形成方法中’係將藉由電子照相法所形成 10 1248564 的帶電潛像而予以顯像、轉印、並定像，然而顯像係適用於磁 1生或非磁性之一成分影像方式，亦適用於二成分顯像方式。’在 -成分顯像方式之影像形成方法的情況下，像調色劑這樣的物 胃係被當做顯像劑來使用；另於二成分顯像方式之影像形成方 ί去@情況下，則係使用調色劑和載體所混合而成之物來做爲顯 像劑。 在本發明之中，使用於影像形成方法中的電子照相用調色 齊!ί ’必須是含有至少一種的環烯烴共聚物樹脂。又，將該調色 劑定像於轉印紙等之記錄媒體的方法，係使用接觸型之加熱壓 著式定像機。在此種定像機之定像組件的表面上，具有含聚苯 并咪唑（以下稱爲「ΡΒΙ」）表層的情況，係特別地合適。定像 組件之形狀可以是輥狀，也可以是帶狀。在定像組件爲輥的情 況下，可以是一種具有藉由塗布而形成含ΡΒΙ表層之物，也可 以是一種將含ΡΒ丨之無縫管裝置在輥上之物。又，在帶的情況 下，可以是一種具有藉由塗布而形成含ΡΒΙ表層之物，也可以 是一種含ΡΒΙ之薄膜這樣的物品。 在使用一種將環烯烴共聚物樹脂用來做爲黏合樹脂之本發 明的電子照相用調色劑，以及使用一種所配備之定像組件爲具 有含ΡΒΙ表層之定像組件的加熱壓著式定像機之影像形成方法 的情況下，即使是在多數枚連續印刷時，也不會發生定像時之 偏位及捲曲現象，並產生可以維持長時期而充分的影像濃度之 效果。又，轉印效率及耐久性均優，而且產生向載體分散最少、 調色劑之消耗量最少、定像組件材料的劣化也最少之效果。 1248564 【實施方式】 【用以實施發明之最佳態樣】 以下，就使用於影像形成方法中的本發明之調色劑予 以詳細地說明。 在本發明中所使用的調色劑，係由至少一種的調色劑 粒子所構成，視情況需要可添加以疏水性矽石爲代表的流 動化劑等。又，調色劑粒子係可藉由含有環烯烴共聚物樹 脂之黏合樹脂，及視情況需要之著色劑、剝離劑、帶電抑 制劑、以及其他的添加劑所構成。 在本發明之調色劑粒子中，黏合樹脂有必要是含有至 少一種的環烯烴共聚物樹脂。環烯烴共聚物樹脂係一種具 有環狀構造之聚烯烴樹脂，例如，乙烯、丙烯、丁烯等之 稀烴（非環式烯烴），與環已烯、正萡烯、四環癸烯等之 具有雙鍵的環烯烴之共聚物，可以是無規共聚物及嵌段共 聚物中之任一種。此等環烯烴共聚物樹脂，可以是藉由使 用如金屬茂系、齊格列系觸媒以公知的聚合方法而製得。 例如’可以利用在特開平5-339327號公報 '特開平5-9223 號公報及特開平6-271 628號公報等所揭示之方法來合成。 在環烯烴共聚物樹脂中α -烯烴和環烯烴之共聚合比， 可以在廣大範圍中變換而適當地設定兩者之投入莫耳比， 藉以得到所期望的物質，具體而言，環烯烴相對於兩者之 總量計宜是設定在2至98莫耳。/。之範圍，較宜是設定在2 至50莫耳。/。之範圍，更宜是設定在2·5至35莫耳％之範圔。 12 1248564 例如，在使乙烯之α -烯烴、正萡烯之環烯烴起反應的情況 下，反應生成物之環烯烴共聚物樹脂的玻璃轉化溫度（Tg)， 係大大地受兩者之投入莫耳比例的影響，當正萡烯之投入 比例增加時，Tg也就有上昇之傾向。具體而言，當正萡烯 之投入比例爲約60重量％時，就會得到Tg差不多爲60至 7〇t之物質。 在本發明中，上述環烯烴共聚物樹脂較宜是以上述之 聚合法所得到的1種物質，又較宜是由平均分子量相異的 複數種物質之混合物。 在本發明之中，較佳的環烯烴共聚物樹脂，舉例來說’ 例如其可以是一種由〇〜75重量％之重量平均分子量（以下 簡稱爲「Mw」）爲小於1 5000之低分子量體、5〜25重量％ 之Mw爲15000〜100000之中分子量體、及20〜95重量％ 之Mw爲超過1 00000之高分子量體的之混合物所構成之物 質。更且，特佳是一種由〇〜70重量％之Mw爲小於15000 之低分子量體、10〜20重量％之Mw爲15000〜100000之中 分子量體、及20〜95重量。/〇之Mw爲超過100000之高分子 量體的混合物所構成之物質。 當上述低分子量體係超過75重量％時，就會變得容易 發生高溫偏位及捲曲現象。又，當上述中分子量體小於5 重量。/。時，就會引起定像組件之捲曲現象及高溫非偏位溫 度之下降；又且，會變得容易使低分子量體和局分子量體 之相溶性變差。當±述之高分子量體係小於2 0重量°/。時’ 13 1248564 就會引起定像組件之捲曲現象及高溫非偏位溫度之下降； 當超過95重量％時，均勻混練性就會變差而造成調色劑性 障礙，又且會有損壞低溫定像性之傾向。 在本發明中，當環烯烴共聚物樹脂係由具有上述3個 不同的重量平均分子量之共聚物的混合物所形成的情況 下，低分子量體較宜是Mw在500〜10 〇〇〇範圍之物，更宜 是Mw在6000〜8000範圍之物。又，中分子量體較宜是Mw 在50000〜90000範圍之物。更且，高分子量體較宜是Mw 爲1 20000以上之物。 另外，在低分子量體多的情況，構成黏合樹脂之主要 部分，並發揮低溫度定像性。中分子量體係在低分子量體 及高分子量體之間時，就會具有使低分子量體和高分子量 體之相溶性增加的功能。高分子量體具有防止高溫偏位、 及向定像輥捲曲之效果。 在本發明中重量平均分子量之測定，係利用GPC測定 法。G P C測定法係如以下所述。也就是說，管柱溫度爲4 〇 °C下以1毫升/分鐘之流速流通四氫呋喃（τ H F)，並注入試 料之T H F溶液來測定，使用聚苯乙烯做爲標物質，然後將 測定値變換爲聚苯乙烯之換算値。 更且，在本發明中，上述環烯烴共聚物樹脂，可以、利 用溶解空氣氧化法、或者藉由馬來酸酐改性或丙烯酸改性 等而導入羧基。藉由這樣，可以提高與其他樹脂間的相溶， 性、顏料之分散性。又，即使藉由已知的方法來導入胺基， 14 1248564 & w μ得到同樣的效果。更且，在環烯烴共聚物樹脂中， 藉著蓝二燦 '環己二烯、四環癸二烯等之二烯單體間的共 ^者在經導入羧基之環烯烴共聚物樹脂中，藉由添 ira胃' _ ' 1¾等之金屬而導入交聯構造，也可以提昇定像 性。 $ 色劑中之環烯烴共聚物樹脂的分子量分布之測 定’係將調色劑溶解在τ η F中之後，以離心分離而採取環 嫌烴共聚物樹脂，然後再以前述的G p C法來進行測定。 在本發明中所使用的環烯烴共聚物樹脂，較宜是充分 地除製造時之十氫化萘的溶劑。殘留在調色劑粒子中的十 氫化萘之濃度，相對於調色劑粒子計，較宜是在500 ppm 以下，更宜是在300 ppm以下。由於十氫化萘是一種高沸 點溶劑歐以容易殘留在調色劑粒子中，當超過500 ppm時 調色劑之帶電抑制能力就變差，而變得容易在印刷影像上 發生白度現象。 又，調色劑中十氫化萘之殘留量的測定方法係爲以質 體層析儀法來進行所得到之値。 在本發明中，黏合樹脂中也可以和上述環烯烴共聚物 樹脂以外的其他樹脂一起倂用。在本發明之中，於黏合樹 脂中環烯烴共聚物樹脂之摻混比例較宜是設定在50〜100重 量之範圍％，更宜是設定在80〜10〇重量％之範圍。當在環 烯烴共聚物樹脂小於50重量°/。的情形下，就會難以提供一 種於多數枚連續影印時’能夠在可能的環境下維持充分的 15 1248564 影像濃度，並且不發生向感光體之薄膜化黑點（黑點現象， 以下稱爲「BS」）及向定像組件熔融附著之問題，以及具有 高顯像性及轉印性之低消費量電子照相用調色劑的傾向。 可與環烯烴共聚物樹脂一起倂用之其他的樹脂，舉例 來說，例如有聚乙烯樹脂、聚丙烯酸酯樹脂、苯乙烯-丙烯 酸酯共聚物樹脂、苯乙烯-甲基丙烯酸酯共聚物樹脂、聚氯 乙烯、聚乙酸乙烯酯、聚氯化亞乙烯、酚醇樹脂、環氧樹 脂、聚酯樹脂、加氫松香、環化橡膠等。特別是就防止調 色劑在定像時之捲曲現象而言，較宜是可以提昇熔融時之 調色劑的黏滯度之物。從而，熔融起始溫度（軟化點）較宜 是某種高程度（例如，120至150。〇之物；又，爲了提昇保 有安定性，較宜是玻璃轉化溫度爲高達65°C以上之物。 在本發明中，爲使得調色劑之低溫定像性及定像時之 離型性向上提昇，較宜是含有臘。特別是在環烯烴共聚物 樹脂之分子量變大的情況下，較宜是爲了補足低溫定像性。 臘’舉例來說，例如聚乙烯臘、聚丙烯臘等之合成臘，鏈 烷烴臘、微晶臘等之石油系臘，巴西棕櫚臘、小燭樹臘、 萊斯臘、硬化芝麻臘等。又，爲了環烯烴樹脂中之臘的微 分散之目的，較宜是使用改性聚乙烯臘。又且，此等臘， 倂用2種以上來使用也可以。調色劑粒子中之臘的含量較 宜是在0.5至10.0重量％之範圍，更宜是在1.〇至8.0重 量％之範圍。當小於0.5重量％時，所賦予的低溫定像性及 定像時之離型性就不夠充分，而當超過10.0重量％時，就 16 1248564 會產生保存安定性方面的問題。 臘雖然可以視情況需要而使用複數種類’然而全部種 類的臘，其以DSC的吸熱波峰所示的熔點較宜是在80°C以 上。當小於80 °C時，就會產生因調色劑粒子之臘而變得容 易引起耐久性之問題。 著色劑方面，可以使用黑色用顏料之碳黑、燈黑；品 紅用顏料之 C · I.顏料紅 1、2、3、4、5、6、7、8、9、1 0、 11、12、13、14、15、16、17、18、19、21、22、23、30、 31、32、37、38、39、40、41、48、49、50、51、52、53、 54、55、57、58、60、63、64、68、81、83、87、88、89、 90、112、114、122、123、163、202、206、207、209 ； C. I.顏料生紅 1 9、C ·丨.生紅 1、2、1 0、1 3、1 5、2 3、2 9、 35等；氫用顏料之C.I.顏料藍2、3、15、16、17，C.I· 顏料隱性藍6，C.I·顏料酸性藍45等；黃用顏料之C.丨.顏 料黃 1、2、3、4、5、6、7、10、11、12、13、14、15、 16、17、23、65、73、74、83、97、155、180 等，此等 係可以單獨使用，混合使用也可以。一般較常使用者，舉 例來說，例如一般俗稱爲碳黑、苯胺藍、鈣油藍、鵝黃、 群青藍、杜邦油紅、喹啉黃、亞甲基藍膠體、酞菁藍、孔 雀藍黃酸鹽、燈黑、羅斯斑卡魯者等。著色劑必須是含有 形成充分的濃度之可見影像所需要的足夠比例，例如，， 相對於1 00重量份之黏合樹脂計宜是在約1至20重量份左 右，較宜是含有1至7重量份左右。 17 1248564 在本發明中所使用的調色劑，較宜是含有視情況需要 之帶電抑制劑。帶電抑制劑係爲了賦予極性而添加之物， 可分爲正電調色劑用和負電調色劑用。可以當做正電調色 劑用者，例如苯胺黑染料、4級銨鹽、吡啶鏺鹽及阿畊等。 又、可以當做負電調色劑用者，例如偶氮系含金屬錯合物、 水楊酸系金屬錯合物及硼系錯合物等；較佳的添加量，相 對於100重量份之黏合樹脂計較宜是0·1至5重量份。又， 此等係可以單獨使用，或使用也沒有關係。在本發明中， 做爲全彩用者較宜是無色；又無色之物，舉例來說，例如 其可以是棚系錯合物、辞錯合物、絡錯合物等，然而較宜 是以下述通式所代表的硼系錯合物，代表性物質爲日本卡 利特公司製之商品名爲L R-1 4 7之市售物。此種硼錯合物相 對於調色劑粒子計較宜是含有1 . 0至4.0重量。/。。[Technical Field] The present invention relates to an electrophotographic toner used in an image forming apparatus such as a copying machine, a printing machine, or a facsimile machine using an electrophotographic technique, and the use of the same The method of image formation. [Prior Art] A dry developer suitable for use in an image of an image forming apparatus of an electrophotographic technique, which can be classified into a two-component system in which a carrier formed of a ferrite iron powder, an iron powder, a glass bead, or the like is mixed. The toner of the image agent and the toner itself contain a magnetic one component image developer of a magnetic powder and a nonmagnetic one component developer. The toner which can be used for such a developer is mainly composed of a binder resin and a coloring agent, and in addition, in order to improve the low-temperature fixing property of the recording paper and the release property of the fixing member, In order to increase the polarity (positive or negative), a charge control agent can also be added. The toner is prepared by mixing the materials at a predetermined blending ratio, and then by a step of dissolving, kneading, grading, and the like, and finally borrowing for controlling fluidity, chargeability, freshness, and preservability. The surface treatment is carried out with additives other than vermiculite, titanium oxide, aluminum oxide, and various resin fine particles, and is supplied as a final developer. As a binder resin for a toner, a styrene-acrylic resin and a polyester resin are mainly used. However, in the case where a styrene-acrylate resin is used as the toner, although the environmental resistance is good, the breaking strength is small so that there is a problem that fine powder is easily generated. Further, the toner using the polyester resin has a problem that the breaking strength is large and the 6 1248564 fine powder is not easily generated, but the environmental resistance is poor. Therefore, the imaging agent currently sold is of course a substance that is concerned with human body and environmental safety and has no substantial problems. However, in recent years, it has tended to select raw materials that are more concerned with human body and environmental safety, and has become an imaging agent. One of the characteristics. In particular, it has become necessary to consider the safety and environmental properties of the adhesive resin which accounts for most of the toner in order to select a constituent monomer and a residual solvent. In the case of such a case, a binder resin for a toner which has been attracting attention recently, for example, a cycloolefin copolymer resin, etc., and a toner using the same are disclosed in Japanese Laid-Open Patent Publication No. Hei 9-101631, No. 2000-284528 Japanese Patent Publication No. 2000-206732 discloses. The monomer of such a resin is safe, and compared with the styrene-acrylate resin, since the true specific gravity is small and the volume specific resistance is also high, development and conversion (transfer efficiency) It is advantageous in that it is excellent, and the number of prints per unit weight is large (the amount of toner is small). Further, since the breaking strength of the resin is large, it is possible to achieve the advantage of lengthening the life of the developer; and it is also very suitable as a resin for the full-shirt toner because of excellent light transmittance. On the other hand, in the fixing machine in which the developer is fixed on the recording medium, the heating and pressing method has gradually become mainstream as the copying speed is increased. In this manner, the transfer paper is passed between the fixing member on the side in contact with the toner and the pressure roller not in contact with the toner, and heat and pressure are simultaneously applied to melt the toner. The method of transferring paper. In this manner, although the fixing member is mostly a set of rollers equipped with a heat source, it is also possible to use a belt such as a heat-resistant film for 7 1248564. On the other hand, the non-contact side of the toner is usually a pressure roller. Further, in order to prevent the molten toner from adhering to the surface of the fixing member at the time of toner fixing, the surface material of the fixing member should be selected for bonding to a styrene-acrylate resin and a polyester resin. The resin can exhibit a substance that is exfoliating. In particular, it is required to have excellent releasability for the fixing member that is in contact with the toner. Representative materials among such releasable materials are "polytetrafluoroethylene (hereinafter referred to as "P T F E") and polyoxymethylene rubber. However, since the heat resistance of such materials is low, it is difficult to set the surface temperature of the fixing member to a high state or to maintain the surface temperature. Since such a result is that the fixing speed of the toner cannot be increased, the increase in the copying speed is limited. Further, the toner of the adhesive resin containing the cyclic olefin copolymer resin is used for a fixing assembly of a general heating press-type fixing machine, and PTFE/polyoxygen oxide, and a polymer for use on the surface of the pressure roller. When a combination of materials such as argon/polyoxygen (image surface/image) is fixed, even if a toner such as a release agent is added, it is inevitable that the image surface will be separated from the fixing member and rolled up. It is the so-called curl phenomenon. Although such a problem can be improved by reducing the amount of the low molecular weight component of the cycloolefin copolymer resin, it is difficult to say that this method is also the best good strategy. As a result, the curling phenomenon cannot be completely solved. In addition, the resin is a phase between a polypropylene, a polyethylene, and a release agent such as a natural wax 8 1248564 which is used for a binder resin for a toner such as a styrene acrylate resin or a polyester resin. Since the solubility is not good, there is a problem that sufficient peeling property cannot be ensured between the fixing member of the release agent. Moreover, since the resin has strong toughness, there is also a problem that the surface of the fixing member is easily worn. On the other hand, in the copiers and printers that have been sold in recent years, the number of consumables tends to be minimized in order to make maintenance easier, and the components that cannot be replaced by the user are increased. It is also one of them. It is necessary for such a component to be inconvenient after a long period of time. However, the fixing machine is an item that is prone to problems, and it is still a problem that often occurs as a result of curling. It is needless to say that it is cumbersome to use, and it is necessary to replace the component by a professional manufacturer, and it has been used in daily use. A problem. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a toner for electrophotography and an image forming method using the same, which is used when a cycloolefin copolymer is used as a binder resin. In the case of a toner, even when a plurality of continuous brushes are used, unevenness and curling phenomenon at the time of fixing do not occur, and good development performance such as long-term and sufficient image density can be maintained. Further, the object of the present invention is Also, it is to provide a toner for electrophotography suitable for full-color images and an image forming method using the same. The toner for electrophotography of the present invention is used for a toner used in a 9 1248564 image forming method using a heat-pressing type fixing machine having a fixing member having a polybenzimidazole-containing surface layer, and is characterized by In the case of an adhesive resin containing at least one cyclic olefin copolymer resin. Further, the toner for electrophotography of the present invention is a binder resin containing a cycloolefin copolymer resin, and the cycloolefin copolymer resin is a low molecular weight having a weight average molecular weight of less than 15,000 by weight of 〇75 to 5% by weight. The mixture is composed of a mixture of 5 to 25% by weight of a weight average molecular weight of 15,000 to 100,000 and a mixture of 20 to 95% by weight of a high molecular weight body having a weight average molecular weight of more than 100,000. Further, the image forming method of the present invention is characterized in that a transfer image of a toner image having a toner for electrophotography using an adhesive resin containing at least one cyclic olefin copolymer resin is supplied thereto. A heated press-fitting machine having a fixing component of a polybenzimidazole containing a surface layer, and then fixing the toner image. Furthermore, an image forming method of the present invention is characterized in that a transfer image of a toner image formed by using an electrophotographic toner containing an adhesive resin containing at least one cyclic olefin copolymer resin is supplied. The toner image is fixed to a heated press-type fixing machine having a fixing member having a polybenzimidazole-containing surface layer, and the cyclic olefin copolymer resin is composed of 〇~75 weight. /. The low molecular weight body having a weight average molecular weight of less than 1 500, 5 to 25 wt% of a weight average molecular weight of 15,000 to 100,000, and 20 to 95 parts by weight. /. It is composed of a mixture of high molecular weight bodies having a weight average molecular weight of more than 100,000. In the image forming method of the present invention, the charged latent image formed by the electrophotographic method is developed, transferred, and fixed, but the image is applied to one of magnetic or non-magnetic. The component image method is also applicable to the two-component imaging method. 'In the case of the image forming method of the component imaging method, the stomach system such as the toner is used as the developer; and in the case of the image formation method of the two component imaging method, A mixture of a toner and a carrier is used as an imaging agent. In the present invention, the coloring for electrophotography used in the image forming method must be at least one type of cycloolefin copolymer resin. Further, a method of fixing the toner to a recording medium such as transfer paper is to use a contact type heating and pressing type fixing machine. It is particularly suitable to have a surface containing a polybenzimidazole (hereinafter referred to as "ΡΒΙ") on the surface of the fixing member of such a fixing machine. The shape of the fixing member may be a roll shape or a belt shape. In the case where the fixing member is a roller, it may be one having a ruthenium-containing surface layer formed by coating, or may be a device in which a seamless tube containing ruthenium is placed on a roll. Further, in the case of a belt, it may be an article having a ruthenium-containing surface layer formed by coating, or may be an article containing a ruthenium-containing film. An electrophotographic toner of the present invention using a cycloolefin copolymer resin as a binder resin, and a fixing assembly equipped with a fixing member having a crucible surface layer In the case of the image forming method of the camera, even in the case of continuous printing of a plurality of pieces, the unevenness and curling phenomenon at the time of fixing do not occur, and an effect of maintaining a sufficient image density for a long period of time is generated. Further, the transfer efficiency and durability are excellent, and the effect of minimizing the dispersion to the carrier, minimizing the consumption of the toner, and minimizing the deterioration of the fixing member material is produced. [Embodiment] [Best aspect for carrying out the invention] Hereinafter, the toner of the present invention used in the image forming method will be described in detail. The toner used in the present invention is composed of at least one kind of toner particles, and a fluidizing agent typified by hydrophobic vermiculite or the like may be added as occasion demands. Further, the toner particles may be composed of a binder resin containing a cyclic olefin copolymer resin, and optionally a color former, a release agent, a charge inhibitor, and other additives. In the toner particles of the present invention, it is necessary that the binder resin contains at least one type of cycloolefin copolymer resin. The cycloolefin copolymer resin is a polyolefin resin having a cyclic structure, for example, a dilute hydrocarbon (acyclic olefin) such as ethylene, propylene or butylene, and a cyclohexene, n-decene, tetracyclononene or the like. The copolymer of a cyclic olefin having a double bond may be any of a random copolymer and a block copolymer. These cycloolefin copolymer resins can be obtained by a known polymerization method using, for example, a metallocene system or a zigzag-type catalyst. For example, it can be synthesized by a method disclosed in Japanese Laid-Open Patent Publication No. Hei. 5-339327, No. Hei. The copolymerization ratio of the α-olefin and the cycloolefin in the cycloolefin copolymer resin can be changed in a wide range and the molar ratio of the two can be appropriately set, thereby obtaining a desired substance, specifically, a cycloolefin relative to The total amount of both is set at 2 to 98 moles. /. The range is preferably set at 2 to 50 moles. /. The range is more preferably set at a range of 2. 5 to 35 mol%. 12 1248564 For example, in the case of reacting a cycloolefin of ethylene α-olefin or n-decene, the glass transition temperature (Tg) of the cycloolefin copolymer resin of the reaction product is greatly affected by both. The effect of the proportion of the ear, when the proportion of the input of n-decene increases, Tg also tends to rise. Specifically, when the proportion of n-decene is about 60% by weight, a substance having a Tg of almost 60 to 7 Torr is obtained. In the present invention, the above cyclic olefin copolymer resin is preferably one which is obtained by the above polymerization method, and more preferably a mixture of a plurality of substances which differ in average molecular weight. In the present invention, a preferred cycloolefin copolymer resin, for example, may be, for example, a low molecular weight body having a weight average molecular weight (hereinafter abbreviated as "Mw") of from 〇 to 75% by weight and less than 15,000. 5 to 25% by weight of Mw is a mixture of 15000 to 100000 of a molecular weight body and 20 to 95% by weight of a mixture of Mw having a high molecular weight of more than 100,000. Further, it is particularly preferably a low molecular weight body having a Mw of less than 15,000 from 〇 to 70% by weight, a Mw of from 10 to 20% by weight, a molecular weight of from 15,000 to 100,000, and a molecular weight of from 20 to 95% by weight. / Mw is a substance composed of a mixture of high molecular weights of more than 100,000. When the above low molecular weight system exceeds 75% by weight, high temperature deviation and curling tend to occur. Further, when the above medium molecular weight body is less than 5 parts by weight. /. At this time, the curling of the fixing member and the decrease in the high-temperature non-biasing temperature are caused, and it becomes easy to deteriorate the compatibility of the low molecular weight body and the local molecular weight body. When the high molecular weight system described by ± is less than 20% by weight. When ' 13 1248564 will cause the curling of the fixing component and the high temperature non-biasing temperature to fall; when it exceeds 95% by weight, the uniform kneading property will be deteriorated, causing toner resistance, and there will be damage to the low temperature. The tendency of fixation. In the present invention, when the cycloolefin copolymer resin is formed of a mixture of copolymers having the above three different weight average molecular weights, the low molecular weight body is preferably a substance having a Mw of 500 to 10 Å. It is more suitable for Mw in the range of 6000~8000. Further, the medium molecular weight body is preferably one having a Mw in the range of 50,000 to 90,000. Further, the high molecular weight body is preferably one having a Mw of 120,000 or more. Further, in the case where the amount of the low molecular weight is large, it constitutes a major part of the binder resin and exhibits low temperature fixing property. When the medium molecular weight system is between a low molecular weight body and a high molecular weight body, it has a function of increasing the compatibility of the low molecular weight body and the high molecular weight body. The high molecular weight body has an effect of preventing high temperature deviation and curling to the fixing roller. In the present invention, the measurement of the weight average molecular weight is carried out by GPC measurement. The G P C assay is as follows. That is to say, the column temperature is 4 / ° C at a flow rate of 1 ml / min. Tetrahydrofuran (τ HF), and the sample is injected into the THF solution to determine, using polystyrene as the standard substance, and then measuring the enthalpy change Converted to polystyrene. Furthermore, in the present invention, the above cyclic olefin copolymer resin may be introduced into a carboxyl group by a dissolved air oxidation method or by maleic anhydride modification or acrylic acid modification. Thereby, the compatibility with other resins and the dispersibility of the pigment can be improved. Further, even if an amine group is introduced by a known method, 14 1248564 & w μ gives the same effect. Further, in the cycloolefin copolymer resin, a common one among the diene monomers such as a blue dibutylene cyclohexadiene or a tetracyclodecadiene is introduced into a cyclic olefin copolymer resin into which a carboxyl group is introduced. It is also possible to improve the fixing property by introducing a crosslinked structure by adding a metal such as ira stomach ' _ ' 13⁄4. Determination of the molecular weight distribution of the cyclic olefin copolymer resin in the toner 'after dissolving the toner in τ η F, taking the ring-like hydrocarbon copolymer resin by centrifugation, and then using the aforementioned G p C method To carry out the measurement. The cycloolefin copolymer resin used in the present invention is preferably a solvent which is sufficiently removed from the production of decalin. The concentration of decalin remaining in the toner particles is preferably 500 ppm or less, more preferably 300 ppm or less, based on the toner particles. Since decalin is a high boiling point solvent, it tends to remain in the toner particles, and when it exceeds 500 ppm, the charge suppressing ability of the toner is deteriorated, and it becomes easy to cause whiteness on the printed image. Further, the method for measuring the residual amount of decalin in the toner is obtained by a mass spectrometry method. In the present invention, the binder resin may be used together with other resins than the above-mentioned cyclic olefin copolymer resin. In the present invention, the blending ratio of the cycloolefin copolymer resin in the binder resin is preferably set in the range of 50 to 100% by weight, more preferably in the range of 80 to 10% by weight. When the cycloolefin copolymer resin is less than 50% by weight. In the case of a large number of consecutive photocopies, it is possible to maintain a sufficient image density of 15 1248564 in a possible environment, and no blackening of the film to the photoreceptor (black spot phenomenon, hereinafter referred to as " BS") and the problem of fusion adhesion to the fixing member, and a tendency to have a low-consumption electrophotographic toner having high developability and transferability. Other resins which can be used together with the cycloolefin copolymer resin are, for example, polyethylene resin, polyacrylate resin, styrene-acrylate copolymer resin, styrene-methacrylate copolymer resin, Polyvinyl chloride, polyvinyl acetate, polyvinyl chloride, phenolic resin, epoxy resin, polyester resin, hydrogenated rosin, cyclized rubber, and the like. In particular, in terms of preventing curling of the toner at the time of fixing, it is preferable to increase the viscosity of the toner at the time of melting. Therefore, the melting initiation temperature (softening point) is preferably a certain degree (for example, 120 to 150. 〇; and, in order to improve the stability, it is preferably a glass transition temperature of up to 65 ° C or more In the present invention, in order to make the low-temperature fixing property of the toner and the release property at the time of fixing upward, it is preferable to contain wax, especially in the case where the molecular weight of the cyclic olefin copolymer resin becomes large. It should be used to supplement the low-temperature fixing property. For example, synthetic waxes such as polyethylene wax and polypropylene wax, petroleum wax such as paraffin wax and microcrystalline wax, Brazilian palm wax, candelilla wax, In the case of the fine dispersion of the wax in the cycloolefin resin, it is preferred to use a modified polyethylene wax. Moreover, it is also possible to use two or more of these waxes. The content of the wax in the toner particles is preferably in the range of 0.5 to 10.0% by weight, more preferably in the range of 1. 〇 to 8.0% by weight. When less than 0.5% by weight, the imparting low-temperature fixing property And the release from fixing is not enough, and when it exceeds 10.0 In the case of %, 16 1248564 will cause problems in preserving stability. Although wax can be used as many times as needed, 'all types of wax, the melting point indicated by the endothermic peak of DSC is preferably 80 ° C. When it is less than 80 ° C, there is a problem that durability is easily caused by the wax of the toner particles. For the coloring agent, carbon black for black pigment, lamp black, and pigment for magenta can be used. C · I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23 , 30, 31, 32, 37, 38, 39, 40, 41, 48, 49, 50, 51, 52, 53, 54, 55, 57, 58, 60, 63, 64, 68, 81, 83, 87 , 88, 89, 90, 112, 114, 122, 123, 163, 202, 206, 207, 209; CI pigment red 1 9 , C · 丨. raw red 1, 2, 1 0, 1 3, 1 5 , 2 3, 2 9, 35, etc.; CI pigment blue 2, 3, 15, 16, 17 for CI, CI·Pigment recessive blue 6, CI·Pigment acid blue 45, etc.; Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14 15, 16, 17, 23, 65, 73, 74, 83, 97, 155, 180, etc. These can be used alone or in combination. Generally, users are more common, for example, commonly known as carbon. Black, aniline blue, calcium oil blue, goose yellow, ultramarine blue, DuPont oil red, quinoline yellow, methylene blue colloid, phthalocyanine blue, peacock blue citrate, lamp black, Rose plaque, etc. The coloring agent must be contained A sufficient ratio to form a sufficient concentration of the visible image is, for example, about 1 to 20 parts by weight, preferably about 1 to 7 parts by weight, based on 100 parts by weight of the binder resin. 17 1248564 The toner used in the present invention is preferably a charge inhibitor which is optionally contained. The charge inhibitor is classified into a positive charge toner and a negative charge toner in order to impart polarity. It can be used as a positively charged toner, such as nigrosine dye, grade 4 ammonium salt, pyridinium salt, and arable. Further, it can be used as a negatively charged toner, for example, an azo-based metal-containing complex, a salicylic acid-based metal complex, a boron-based complex, and the like; a preferred addition amount is bonded to 100 parts by weight. The resin is preferably from 0.1 to 5 parts by weight. Also, these systems can be used alone or in use. In the present invention, as a full-color user, it is preferably colorless; and colorless, for example, it may be a shed complex, a complex, a complex, etc., but it is preferably The boron-based complex represented by the following formula is a commercially available product of the trade name L R-1 4 7 manufactured by Kali Corporation, Japan. The boron complex is preferably contained in an amount of from 1.0 to 4.0 by weight based on the toner particles. /. .
(式中’R1及R4係代表氫原子、焼基、取代或未取 代的芳香環（包括縮合環），R2及R3係代表取代或未取代 的芳香環（包括縮合環），Β代表硼原子，χη +代表陽離子， 18 1248564 帶電組件上，因而容易產生影像缺陷。當超過3_0重量％時， 則疏水性矽石容易發生脫落，並引起感光體上的BS等之問 題。又，疏水性矽石微粒子較宜是使用由大粒徑、中、小 粒徑所組合而成之物。藉由利用此種外部添加配方，可以 得到更爲安定的耐熔著特性。 所謂之大粒徑係指粒徑在0.03至0.10微米之物。而 所謂的中、小粒徑則係指小於0.03微米之物。當大粒徑疏 水性矽石超過0.1 0微米時，流動性就會變差，而當小於0.03 微米時就得不到充分之耐熔著性。中、小粒徑之疏水性矽 石係爲擔任保持調色劑在一定以上之流動性的角色。 就調色劑來說，除了疏水性矽石微粒子以外，爲了控 制調色劑之流動性、帶電性、洗淨性、及保存性等之目的， 也可以使附著有磁性粉、氧化鋁、滑石、瓷土、碳酸鈣、 碳酸鎂、氧化鈦、或者各種的樹脂微粒子等之矽石微粒子 以外的外添加劑。 爲使上述微粒附著在調色劑粒子上，舉例來說，例如 利用透平攪拌機、亨歇魯混合機、超混合機等之一般的攪 拌機予以混合、攪拌等之方法。 接著’說明在本發明之影像形成方法中所使用的加熱 壓著式定像機。如以上所述’使用含有以環烯烴共聚物樹 脂做爲黏合樹脂之調色劑時，容易在加熱壓著式定像機上 引起捲曲。本發明人等爲了防止當使用含有以環烯烴共聚 物樹脂做爲黏合樹脂之調色劑時加熱壓著式定像機的捲曲 20 1248564 現象，因而從定像組件方面開始銳意檢討起 定像組件上具有含Ρ B I之表層的物質時可 象，並辨明對於環烯烴共聚物樹脂而言PBI 異的離型性。 在本發明中，係使用在定像組件之表面 的表面層之物來做爲加熱壓著式定像機。不 劑非接觸側之加壓輥表面、及耐熱性或耐磨 PBI也可以。定像組件之形狀一般有輥狀和帶 PBI係爲如下述通式所示的超耐熱•高 膠，使用PBI之加熱壓著式定像機，係爲 2984404號公報及特許3261 1 66號公報上所j ，發現使用在 以防止捲曲現 係具有特別優 上具有含ΡΒΙ 用說，在調色 耗性之面含有 機能性工程塑 如在日本特許 魯示者。(wherein R1 and R4 represent a hydrogen atom, a fluorenyl group, a substituted or unsubstituted aromatic ring (including a condensed ring), R2 and R3 represent a substituted or unsubstituted aromatic ring (including a condensed ring), and fluorene represents a boron atom. , χ η + represents a cation, 18 1248564 on a live component, and thus is prone to image defects. When it exceeds 3 _0% by weight, the hydrophobic vermiculite is liable to fall off and cause problems such as BS on the photoreceptor. Preferably, the stone particles are composed of a combination of large particle diameters, medium and small particle diameters, and by using such an externally added formulation, a more stable refractory resistance property can be obtained. The particle size is in the range of 0.03 to 0.10 μm, and the so-called medium and small particle size means less than 0.03 μm. When the large particle size hydrophobic meteorite exceeds 0.1 0 μm, the fluidity will deteriorate, and when When the thickness is less than 0.03 μm, sufficient refractory resistance is not obtained. The hydrophobic vermiculite of medium and small particle size serves to maintain the fluidity of the toner at a certain level or more. In terms of toner, in addition to hydrophobicity Beyond the meteorite particles, in order to The magnetic powder, alumina, talc, china clay, calcium carbonate, magnesium carbonate, titanium oxide, or various resins may be attached for the purpose of controlling the fluidity, chargeability, detergency, and preservability of the toner. An external additive other than the fine particles of fine particles such as fine particles, etc., in order to adhere the fine particles to the toner particles, for example, by using a general mixer such as a turbo mixer, a Henschel mixer, or an ultra mixer, A method of stirring and the like. Next, a description will be given of a heated press-type fixing machine used in the image forming method of the present invention. When the toner containing a cycloolefin copolymer resin as a binder resin is used as described above, It is easy to cause curling on a heated press-type fixing machine. The present inventors have tried to prevent the phenomenon of curling 12 1248564 of a press-type fixing machine when using a toner containing a cyclic olefin copolymer resin as a binder resin, Therefore, from the aspect of the fixing assembly, it is possible to review the material having the surface layer containing Ρ BI on the fixing member, and to discriminate PB for the cyclic olefin copolymer resin. In the present invention, the surface layer of the surface of the fixing member is used as a heated press-type fixing machine, the surface of the pressure roller which is not on the non-contact side, and heat resistance. Or the wear-resistant PBI is also available. The shape of the fixing unit is generally a roll shape and a belt PBI is a super heat-resistant and high-glue as shown in the following general formula, and a heating press-type fixing machine using PBI is the bulletin 2984404. And it was found that it was used in the Japanese Patent No. 3261 1 66, and it was found that it was used in the prevention of curling, and it was used in Japan.
(式中，R爲氫原子或烷基）。 P B I係耐熱性顯著高於向來被使用於定 之PTFE及聚矽氧橡膠之物。因此結果，熱 可以高些，所以可提高複印速度。又，PBI 良’係爲一種適合於做爲轉印紙以高速通過 在本發明中所使用的PBI之數平均分子量較:ί 像組件表面上 輥之設定溫度 的耐磨耗性優 之輥的材質。 [是在2000至 21 1248564 100000之範圍，更宜是在5000至30000之範圍。 使用在電子照相式複印機及印刷機用之加熱壓著式定 像機上的定像組件之含有P B I的表層之組成，可以單獨地 使用PBI，然而在像下述的情況下，可以使之含有他的材 料。但是，在任何一種的情形下PBI較宜是在50重量％以 上。當PBI之含量小於50重量％時，就不能夠發揮PBI的 耐熱性、耐磨耗性、對環烯烴共聚物樹脂之離型性的特徵。 例如，由於P B I會有因壓縮彈性模數及拉伸彈性模數 稍小的定像條件而伸縮的情形，所以在此種情況下使之含 有一具有比較大的耐熱性樹脂，例如含有聚醯亞胺可以使 得彈性模數變大。 又，像在比較要求離型性的情況下，也以使之含有高 分子氟化合物或低分子氟化合物。 上述高分子氟化合物係指含有氟之單一聚合物或共聚 物’或者是含有氟之單體與其他的單體間之共聚物。此種 高分子氟化合物’有聚四氟乙烯、聚三氟氯化乙烯、聚氟 化乙烯、聚氟化亞乙烯、聚二氯二氟乙烯等。此等之中， 較宜是使用聚四氟乙烯。 在本發明中所謂的低分子氟化合物，係指含有氟原子 之無機或有機化合物。較佳的分子氟化合物，係含有碳原 子數小於2 0之氟化碳氫化合物。上述之氟化碳氫化合物， 可以爲其他的所取代之物，例如，以烷氧基、炔基、芳基、 氧基、氫氧基、羧基、醯基、胺基、硝基、鹵素等所取代 22 1248564 者。 又’在本發明中，定像組件的含有PBI之表層上，也 可以同時含有上述高分子氟化合物及低分子氟化合物。 更且，在本發明中，定像組件的含有p B丨之表層上， 含有添加上述氟化合物之內添加塡料也可以。使含PB丨表 層內含有內添加塡料，可以提高PBI的自身潤滑性及電傳 導性。條這樣的內添加塡料，舉例來說，例如SiC、各種 金屬粉末及石墨等之碳。藉提昇自身潤滑性以改善定像組 係中複印紙的通紙性，而藉著提昇電傳導性可以防止定像 組件、轉印紙、調色劑間因摩擦而產生的靜電、並防止其 累積。 又，PBI之表面硬度以洛氏硬度K級計爲1 10，係非 常地硬，在不恰當的情況下，可藉由在含P B I表層內使含 有黏合樹脂物質來改善彈性及表面硬度。藉著改善彈性及 表面硬度，可使定像組件材料間之接觸面積，即在噴嘴幅 度上所持有的之自由度，而可以控制調色劑之定像效率。 此種黏合樹脂物質，舉例來說，例如 HTV(高溫硫化）聚砂 氧橡膠、RTV(室溫硫化）聚矽氧橡膠、LTV(低溫硫化）聚矽 氧橡膠。 以下，以圖來說明使用在本發明之影像形成方法的加 熱壓著式定像機中之具有含PBI表層的定像組件之例子。 但，本發明不受限於此等之物而已。 第1圖係爲在加熱壓著式定像機中的定像組件爲輥之 23 1248564 情況。定像輥彳係在銘製芯管3之表面上設有含p b I之表 層2，又在中心處具有將調色劑予以定像用的熱源4。在定 像輥之對向上設有加壓輥5，此等輥係依照箭頭方向旋轉。 定像係藉由將調色劑影像7被形成的轉印紙6插入定像車昆 和加壓輥之間來進行。 第2圖係定像組件爲帶之情況。在圖中，由p B丨所形 成的薄膜（或在聚醯亞胺薄膜等之底膜上設置PB丨含有表層 的薄膜）的帶8係懸架在支撐輥及驅動輥上，按照箭頭方向 旋轉。在此帶的裡面上係設置有內接的熱源4，又在其對 向位置上設置加壓輥5。定像係藉由將調色劑影像7被形 成的轉印紙6插入在熱源4和加壓輥5間移動的帶和加盤 輥之間來進行。 使用於在本發明中加熱壓著式定像機之含有PBI的表 層之定像組件，爲了使P B I溶解於溶劑中，可以藉由在視 情況需要而均一地添加其他的物質之後，將之塗布在芯管 和撓性帶上製造而得。也就是說，使芯管或帶浸鍍含PBI 液體，或者於芯管之表面上噴灑而鍍上PBI，然後藉由將 溶劑乾燥而得到目的之定像組件。上述之溶劑，舉例來說， 例如可以從使用以N，N-二甲基乙醯胺、N，N-二甲基甲醯胺、 二甲基磺醯胺及N-甲基-2-吡咯烷酮爲起始所製的PBI之乾 式紡紗液所用的溶劑中選取。特佳的溶劑爲N , N-二甲基乙 醯胺、N-甲基-2-吡咯烷酮。又，在帶的情況下，也可以是 如第2圖所示之含有PBI的薄膜。 24 1248564 又，可使用於在本發明之加熱壓著式的定像機定像組 件，係可以將含有PB丨之混合物燒結成圓筒狀而形成，又 可以在燒結成形後加工成圓筒狀製造而得。PBI雖然長熱 可塑性樹脂，然而由於熔點爲比分解點高的緣故，所以不 能施行熔融擠壓成形加工。從而，就製造成形體而言，係 將PBI等之粉體予以燒結而得到成形體。 藉由使用 P B I，則可以發揮比在習用的加熱壓著式定 像機上所使用的組件更高的耐熱性、耐磨耗性，即使與以 含有樹脂強度強的環烯烴共聚物做爲主要黏合樹脂的調色 劑組合時，也可以使定像組件的壽命變得極長，而且在定 像機上也不捲曲。從而，可以將調色劑接觸側之定像組件 的表面溫度設定在高位，而且由於環烯烴共聚物樹脂之離 型性優異的緣故，從而可以達成複印速度高速化之目的。 又，P B I較宜是具有經疏水化處理的聚苯并咪唑（以下， 稱爲「N - P B I」），未經疏水化處理的P B I係爲不使用於印 刷機時會引起水分吸附，而於使用時放出吸分，因爲這樣 的循環而容易劣化，使得壽命變得比經疏水化之物短，因 而有損壞適用於定像組件的傾向。N-PBI雖然是可以從上 述通式中R爲代表烷基之物中選取，然而較爲合適之物是 CH3 或 C2H5 〇 【實施例】 以下，以實施例和比較例爲基礎來說明本發明。但是， 本發明並不因此而限定於此事物而已。 25 1248564 <環烯烴共聚物樹脂之製作> 將下述之低分子量體、中分子量體、高分子量體以預 定的比率熔融混合，並製成九粒化之環烯烴共聚物樹脂。 任何一種均是經以帝可納社製，商品名：TOP AS，充分地 進行除去殘留溶劑後的型態。 •低分子量體（產品編號：TM) ; Mw爲7000 •中分子量體（產品編號：8007); Mw爲80000 •高分子量體（產品編號：TB); Mw爲140000 <環烯烴共聚物樹脂A之製作> 將上述之34重量％的TM、10重量％之8007、56重量 %之T B予以熔融混合，並經九粒化後做成環烯烴共聚物樹 脂A 〇 <環烯烴共聚物樹脂B之製作> 將上述之62重量％的TM、10重量。/。之8007、28重量 %之T B予以熔融混合，並經九粒化後做成環燦煙共聚物樹 脂B。 <環烯烴共聚物樹脂C之製作〉 將上述之20重量。/。之8007、80重量。/°之丁8予以溶融 混合，並經九粒化後做成環烯烴共聚物樹脂C ° <調色劑之製作> 【實施例1】（調色劑A之製作） 84重量份(wherein R is a hydrogen atom or an alkyl group). The heat resistance of the P B I system is remarkably higher than that of the conventionally used PTFE and polyoxymethylene rubber. As a result, the heat can be made higher, so the copying speed can be increased. Further, the PBI is a material suitable for use as a transfer paper for high-speed passage of the PBI used in the present invention. The average molecular weight of the PBI is higher than that of the roll at the set temperature of the surface of the component. . [It is in the range of 2000 to 21 1248564 100000, more preferably in the range of 5000 to 30,000. PBI can be used singly in the composition of the PBI-containing surface layer of the fixing unit on the electrophotographic copying machine and the heating press-type fixing machine for the printing machine. However, in the case of the following, it can be contained. His material. However, in either case, the PBI is preferably 50% by weight or more. When the content of PBI is less than 50% by weight, the heat resistance and abrasion resistance of PBI and the release property to the cycloolefin copolymer resin cannot be exhibited. For example, since PBI has a tendency to expand and contract due to a compression elastic modulus and a fixing condition in which the tensile elastic modulus is slightly smaller, in this case, it is required to contain a relatively large heat resistant resin, for example, containing polyfluorene. The imine can make the elastic modulus larger. Further, in the case where the release property is required to be comparatively, it is also required to contain a high molecular fluorine compound or a low molecular fluorine compound. The above polymer fluorine compound means a single polymer or copolymer containing fluorine or a copolymer of a monomer containing fluorine and another monomer. Such a polymer fluorine compound 'is polytetrafluoroethylene, polytrifluoroethylene chloride, polyfluorinated ethylene, polyfluorinated ethylene, polydichlorodifluoroethylene or the like. Among these, it is preferred to use polytetrafluoroethylene. The "low molecular fluorine compound" as used in the present invention means an inorganic or organic compound containing a fluorine atom. A preferred molecular fluorine compound is a fluorinated hydrocarbon having a carbon number of less than 20%. The above-mentioned fluorinated hydrocarbon compound may be other substituted substances, for example, an alkoxy group, an alkynyl group, an aryl group, an oxy group, a hydroxyl group, a carboxyl group, a decyl group, an amine group, a nitro group, a halogen group, or the like. Replaced 22 1248564. Further, in the present invention, the surface layer containing PBI of the fixing member may contain both the polymer fluorine compound and the low molecular fluorine compound. Further, in the present invention, the surface layer containing p B 定 of the fixing member may contain an internally added mash added with the above fluorine compound. By including the internally added mash in the surface layer containing PB, the self-lubricity and electrical conductivity of PBI can be improved. Such an internal additive is, for example, carbon such as SiC, various metal powders, and graphite. By improving the self-lubricity to improve the paper-passing property of the copy paper in the fixing group, by increasing the electrical conductivity, the static electricity generated by the fixing component, the transfer paper, and the toner due to friction can be prevented and prevented from accumulating. . Further, the surface hardness of PBI is 1 10 in terms of Rockwell hardness K grade, which is very hard, and if it is not appropriate, the elasticity and surface hardness can be improved by including a binder resin substance in the surface layer containing P B I . By improving the elasticity and surface hardness, the contact area between the fixing member materials, that is, the degree of freedom held in the nozzle width, can be controlled to control the fixing efficiency of the toner. Such a binder resin material is, for example, HTV (high temperature vulcanization) polyoxyethylene rubber, RTV (room temperature vulcanization) polyoxymethylene rubber, LTV (low temperature vulcanization) polyoxymethylene rubber. Hereinafter, an example of a fixing member having a PBI-containing surface layer used in the heating and press-type fixing machine of the image forming method of the present invention will be described with reference to the drawings. However, the invention is not limited to these. Figure 1 shows the case where the fixing assembly in the heated press-type fixing machine is the roller 23 1248564. The fixing roller is provided with a surface layer 2 containing p b I on the surface of the ingot core tube 3, and a heat source 4 for fixing the toner at the center. Pressing rolls 5 are provided in the opposite direction of the fixing roller, and these rolls are rotated in the direction of the arrow. The fixing is performed by inserting the transfer paper 6 formed by the toner image 7 between the fixing car and the pressure roller. Figure 2 shows the case where the fixing component is a belt. In the figure, a belt 8 formed of p B ( (or a film containing a surface layer of PB 在 on a base film of a polyimide film or the like) is suspended on a support roller and a driving roller, and is rotated in the direction of the arrow. . An internal heat source 4 is disposed on the inside of the belt, and a pressure roller 5 is disposed in the opposite position. The fixing is performed by inserting the transfer paper 6 formed by the toner image 7 between the belt moved between the heat source 4 and the pressure roller 5 and the pad roller. In the present invention, the fixing unit of the PBI-containing surface layer of the press-type fixing machine is heated, and in order to dissolve the PBI in the solvent, it may be coated by uniformly adding other substances as occasion demands. Made on core and flexible strips. That is, the core tube or tape is immersed in a PBI-containing liquid, or sprayed on the surface of the core tube to be plated with PBI, and then the target fixing member is obtained by drying the solvent. The above solvent can be, for example, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfonamide and N-methyl-2-pyrrolidone. It is selected from the solvents used for the dry spinning solution of the PBI produced. Particularly preferred solvents are N,N-dimethylacetamide, N-methyl-2-pyrrolidone. Further, in the case of a belt, a film containing PBI as shown in Fig. 2 may be used. 24 1248564 Further, the fixing assembly for the fixing and pressing type of the present invention can be formed by sintering a mixture containing PB crucible into a cylindrical shape, or processing into a cylindrical shape after sintering. Made by. Although PBI has a long thermoplastic resin, since the melting point is higher than the decomposition point, the melt extrusion molding process cannot be performed. Therefore, in the production of a molded body, a powder such as PBI is sintered to obtain a molded body. By using PBI, it is possible to exert higher heat resistance and wear resistance than the components used in conventional heated press-type fixing machines, even if it is mainly composed of a cyclic olefin copolymer containing a strong resin. When the toner combination of the binder resin is combined, the life of the fixing unit can be made extremely long and it is not curled on the fixing machine. Therefore, the surface temperature of the fixing unit on the toner contact side can be set to a high level, and since the release property of the cycloolefin copolymer resin is excellent, the object of speeding up the copying speed can be achieved. Further, PBI is preferably a hydrophobized polybenzimidazole (hereinafter referred to as "N-PBI"), and the PBI which is not hydrophobized causes moisture adsorption when not used in a printing machine. The absorption is released at the time of use, and is easily deteriorated by such a cycle, so that the life becomes shorter than that of the hydrophobized material, and thus there is a tendency that damage is applied to the fixing member. Although N-PBI can be selected from the above formula wherein R is a representative alkyl group, a suitable one is CH3 or C2H5 〇. [Examples] Hereinafter, the present invention will be described based on examples and comparative examples. . However, the present invention is not limited to this. 25 1248564 <Preparation of a cycloolefin copolymer resin> The following low molecular weight, medium molecular weight, and high molecular weight bodies are melt-mixed at a predetermined ratio to obtain a nine-part cycloolefin copolymer resin. Any one of them is a type in which the residual solvent is sufficiently removed by the product name: TOP AS, manufactured by Dikona. • Low molecular weight (product number: TM); Mw is 7000 • Medium molecular weight (product number: 8007); Mw is 80,000 • High molecular weight (product number: TB); Mw is 140000 < cycloolefin copolymer resin A Preparation> The above-mentioned 34% by weight of TM, 10% by weight of 8007, and 56% by weight of TB are melt-mixed, and after granulation, a cyclic olefin copolymer resin A 〇 < cycloolefin copolymer resin is obtained. Production of B> The above-mentioned 62% by weight of TM and 10 parts by weight. /. The 8007 and 28% by weight of T B were melt-mixed, and after nine granulations, the ring-flavored copolymer resin B was obtained. <Production of Cyclic Olefin Copolymer Resin C> The above 20 weight. /. 8007, 80 weight. / ° butyl 8 is melted and mixed, and after nine granulation, it is made into a cyclic olefin copolymer resin C ° <Production of Toner> [Example 1] (Production of Toner A) 84 parts by weight
•環烯烴共聚物樹脂A 26 1248564 •聚丙烯臘 7重量份 (三洋化成工業公司製、商品名：畢可魯660P、熔點137。〇 硼錯合物 2重量份 (日本卡利特公司製、商品名：LR· 147) 碳黑 7重量份 (卡卜特公司製、商品名REGUL330R) 將由上述之摻混比所形成的原料以超混合機予以混 合’並在雙軸擠壓中熔融混練後，以噴射式硏磨機予以粉 碎’然後再以乾式氣流分級機進行分級，而得到體積平均 粒徑爲9微米之調色劑粒子。 然後，在此調色劑中添加〇 · 3重量％之大粒徑疏水性矽 石（日本愛羅迪魯公司製、商品名·· NA-50Y，粒徑爲0.050 微米）、和1 ·0重量％之中粒徑疏水性矽石（瓦卡化學公司製、 商品名：H2000/4M，粒徑爲0.015微米），於亨歇魯混合 機中以40公尺/秒之周速混合4分鐘而得到調色劑A。調 色劑粒子中十氫化萘的殘留濃度爲95 ppm。 【實施例2】（調色劑B之製作） 除了使用環烯烴共聚物樹脂B以代替環烯烴共聚物樹 月旨A以外，均和實施例1同樣的做法而製得調色劑B。調 色劑粒子中的十氫化萘之殘留濃度爲250 ppm。 【實施例3】（調色劑C之製作） 除了使用環烯烴共聚物樹脂C以代替環烯烴共聚物樹 27 1248564 脂A以外，均和實施例1同樣的做法而製得調色劑C °調 色劑粒子中的十氫化萘之殘留濃度爲75 ppm ° 比較用調色劑之製作例（調色劑〇之製作） 除了使用聚酯樹脂（三菱麗陽公司製、商品名：FC-1 142) 以代替環烯烴共聚物樹脂A以外，均和實施例1同樣的做 法而製得調色劑D。 <具有含PBI表層之定像輥之製作> (定像輥a之製作） 將N-PBI (克拉瑞日本公司製）溶解於N，N-二甲基乙醯 胺而得到塗布液。藉由利用噴灑法將此、塗布液塗布在鋁製 的直徑爲20毫米之芯管表面上。接著，將此塗布膜在 320°C下燒成，而得到具有薄膜厚度爲20微米之N-PBI薄 膜的定像輥a。 (定像輥b之製作） 將N-PBI (克拉瑞日本公司製）、和聚醯胺（杜邦公司製、 商品名：貝斯貝魯）溶解於N，N-二甲基乙醯胺而得到塗布 液。藉由利用噴灑法將此塗布液塗布在鋁製的直徑爲20毫 米之芯管表面上。接著，將此塗布膜在320 °C下燒成，而得 到具有薄膜厚度爲20微米之N-PBI薄膜的定像輥b。 【實施例4至6、比較例1】 前述實施例1至3及比較用之各種調色劑（調色劑A至 D )、和聚矽氧塗布肥粒鐵載體（平均粒徑爲8 0微米）予以混 合，使調色劑/載體重量比率成爲5/95的雙成分顯像劑。 28 1248564 將此種顯像劑使用在安裝有經以p B1被覆的定像輥a之夏 普公司製複印機AR-S400之定像輥上’於溫度25°C/溼度 5 0 %之環境下，影像比率爲5 %之A4原稿複印在1 0萬張A4 轉印紙上，分別評量影像濃度（丨D )、白度差（B G )、偏位及 捲曲、分散量、調色劑消耗量、轉印效率。 【實施例7】 前述實施例1之調色劑A、和聚矽氧塗布肥粒鐵載體（平 均粒徑爲80微米）予以混合，使調色劑/載體重量比率成爲 5/95的雙成分顯像劑。將此種顯像劑使用在安裝有經以N_ PBI和聚醯亞胺被覆的定像輥b之夏普公司製複印機AR-S400之定像輥上，於溫度25°C/溼度50%之環境下，影像 比率爲5%之A4原稿複印在1 0萬張A4轉印紙上，分別評 量影像濃度（ID)、白度差（BG)、偏位及捲曲、分散量、調 色劑消耗量、轉印效率。 【比較例2至4】 前述實施例1、3及比較用之調色劑A、C及D、和聚 矽氧塗布肥粒鐵載體（粒徑爲80微米）予以混合，使調色劑/ 載體重量比率成爲5/95的雙成分顯像劑。將此種顯像劑使 用在調色劑接觸側之定像輥之材質爲由PTFE所構成的夏 普公司製複印機AR-S400之定像輥上，於溫度25°C/溼度 50%之環境下，影像比率爲5%之A4原稿複印在10萬張之 A4轉印紙上，分別評量影像濃度（id)、白度差（BG)、偏位 及捲曲、分散量、調色劑消耗量、轉印效率。 29 1248564 評量方法係如下所述。 1 .影像濃度（丨D )係以馬可貝斯反射濃度計r d - 9 1 4測定冷影 像部而得。 2_白度差（BG)係以曰本電色工業公司製之色彩計ze 20 00 測角非影像部之白色度，以複印前後之白色度差表示。 3 .偏位及捲曲係以目視確認。 A:不發生偏位及捲曲； B :在影像面上出現高溫或低溫偏位之徵兆； C:發生明顯的偏位或捲曲。 4 ·向載體之分散量係將顯像劑陂入界面活性劑水溶液中予 以洗淨，除去調色劑，並將殘留的載體予後乾燥後，於 堀場製作所製的碳分析儀（商品名：EMIA-110)中測角未 使用的載體和耐刷試驗後之載體的碳重量，由其差値求 得附著在載體上的碳重量，以重量°/。表示/。 5 .調色劑消耗量係由調色劑之減少量而求得。 6 _轉印效率係消耗調色劑量當做A、回收調色劑量當做b， 以下式而得。 〔（A-B)/A〕X 1 00% 評量結果如表1所示。 30 1248564• Cyclic olefin copolymer resin A 26 1248564 • 7 parts by weight of polypropylene wax (manufactured by Sanyo Chemical Industries, Ltd., trade name: kekelu 660P, melting point 137. bismuth boron complex 2 parts by weight (manufactured by Japan Carlyle Co., Ltd.) Trade name: LR· 147) 7 parts by weight of carbon black (manufactured by Kabate Co., Ltd., trade name: REGUL330R). The raw materials formed by the above blending ratio are mixed by an ultra-mixer' and melt-kneaded in biaxial extrusion. And pulverized by a jet honing machine' and then classified by a dry gas flow classifier to obtain toner particles having a volume average particle diameter of 9 μm. Then, 3% by weight of the toner was added to the toner. Large-diameter hydrophobic vermiculite (manufactured by Irodru, Japan, trade name · NA-50Y, particle size: 0.050 μm), and 1% by weight of medium-sized hydrophobic meteorites (Waka Chemical Co., Ltd.) System, trade name: H2000/4M, particle size 0.015 μm), mixed in a Henschel mixer at a peripheral speed of 40 m/s for 4 minutes to obtain Toner A. Decalin in the toner particles The residual concentration was 95 ppm. [Example 2] (Production of Toner B) Toner B was obtained in the same manner as in Example 1 except that the cycloolefin copolymer resin B was used instead of the cycloolefin copolymer tree A. The residual concentration of decalin in the toner particles was 250. [Example 3] (Production of Toner C) A toner was obtained in the same manner as in Example 1 except that the cycloolefin copolymer resin C was used instead of the cycloolefin copolymer tree 27 1248564. Residual concentration of decalin in the C ° toner particles is 75 ppm ° Production example of the comparative toner (production of toner )) In addition to polyester resin (Mitsubishi Laiyang Co., Ltd., trade name: FC) -1 142) A toner D was obtained in the same manner as in Example 1 except for the cycloolefin copolymer resin A. <Preparation of a fixing roller having a PBI surface layer> (Fixing roller a) (manufactured) N-PBI (manufactured by Kerry Japan Co., Ltd.) was dissolved in N,N-dimethylacetamide to obtain a coating liquid, and the coating liquid was applied to an aluminum glass having a diameter of 20 mm by a spraying method. On the surface of the core tube. Then, the coated film was fired at 320 ° C to obtain Fixing roller a of N-PBI film having a film thickness of 20 μm (Production of fixing roller b) N-PBI (manufactured by Clarisse Japan Co., Ltd.) and polydecylamine (manufactured by DuPont, trade name: Beth Bay) The coating liquid was obtained by dissolving in N,N-dimethylacetamide, and the coating liquid was applied on the surface of a core tube of 20 mm in diameter by a spray method. Then, the coating film was placed thereon. The film was fired at 320 ° C to obtain a fixing roller b having an N-PBI film having a film thickness of 20 μm. [Examples 4 to 6, Comparative Example 1] The above Examples 1 to 3 and various kinds of color matching were used. The toner (Toner A to D) and the polyoxynitride-coated ferrite carrier (having an average particle diameter of 80 μm) were mixed so that the toner/carrier weight ratio became a two-component developer of 5/95. 28 1248564 The developer is used in a setting roller of a Sharp Co., Ltd. copier AR-S400 equipped with a fixing roller a coated with p B1 at a temperature of 25 ° C / humidity of 50%. A4 originals with an image ratio of 5% were copied on 100,000 sheets of A4 transfer paper, and the image density (丨D), whiteness difference (BG), offset and curl, dispersion amount, toner consumption, Transfer efficiency. [Example 7] The toner A of the foregoing Example 1 and the polyoxynitride coated iron carrier (average particle diameter of 80 μm) were mixed so that the toner/carrier weight ratio became a two-component of 5/95. Imaging agent. This developer was used on a fixing roller of a Sharp Co., Ltd. copier AR-S400 equipped with a fixing roller b coated with N_PBI and polyimide, at a temperature of 25 ° C / humidity of 50%. Next, A4 originals with an image ratio of 5% were copied on 100,000 sheets of A4 transfer paper, and the image density (ID), whiteness difference (BG), offset and curl, dispersion amount, and toner consumption were evaluated. Transfer efficiency. [Comparative Examples 2 to 4] The foregoing Examples 1 and 3 and the comparative toners A, C and D, and the polyoxynitride-coated ferrite iron carrier (having a particle diameter of 80 μm) were mixed to make a toner/ The carrier weight ratio became a two-component developer of 5/95. The fixing agent used for the fixing roller on the toner contact side is made of a fixing roller of a Sharp Co., Ltd. copier AR-S400 made of PTFE, at a temperature of 25 ° C / humidity of 50%. A4 originals with an image ratio of 5% were copied on 100,000 sheets of A4 transfer paper, and the image density (id), whiteness difference (BG), offset and curl, dispersion amount, toner consumption, Transfer efficiency. 29 1248564 The assessment method is as follows. 1. The image density (丨D) is obtained by measuring the cold image portion by the Marcobes reflection densitometer r d - 9 1 4 . 2_Whiteness difference (BG) is the whiteness of the non-image section of the color meter ZE 20 00 produced by Sakamoto Photoelectric Industries Co., Ltd., which is expressed by the difference in whiteness before and after copying. 3. The offset and curl are visually confirmed. A: no deviation and curling occurs; B: signs of high temperature or low temperature deviation on the image surface; C: significant deviation or curl occurs. 4 · Dispersion amount to the carrier The developer is added to the surfactant aqueous solution to be washed, the toner is removed, and the remaining carrier is dried, and then a carbon analyzer manufactured by Horiba, Ltd. (trade name: EMIA) -110) The carbon weight of the carrier which is not used in the middle angle measurement and the carrier after the brush resistance test, and the weight of the carbon attached to the carrier is determined by the difference, by weight /. Indicates /. 5. The toner consumption amount is determined from the amount of reduction of the toner. 6 _ Transfer efficiency is the consumption of the toner amount as A, the recovery toner amount as b, the following formula. [(A-B)/A] X 1 00% The evaluation results are shown in Table 1. 30 1248564
實施例 實施例 實施例 實施例 比較例 比較例 比較例 比較例 4 5 6 7 1 2 3 4 黏合樹脂 COC COC COC COC PES COC COC PES 調色劑 A B C A D A C D 定像輥 PBI PBI PBI PBI/ PBI PTFE PTFE PTFE 醯亞胺 ID 初期 1 .48 1.53 1 .41 1 .45 1.42 因捲 因捲 1.44 2萬張 1 .47 1.55 1 .42 1 .46 1.40 曲而 曲而 1.44 4萬張 1 .47 1.53 1 .40 1 .46 1 .42 無法 無法 1 .43 6萬張 1 .46 1 .52 1.42 1.47 1.35 評量 評量 1.36 8萬張 1.48 1 .54 1 .42 1 .45 1.31 1 .34 10萬張 1 .47 1 .55 1 .41 1 .45 1.25 1 .27 BG 初期 0.33 0.38 0.41 0.38 0.52 因捲 因捲 0.59 2萬張 0.35 0.37 0.38 0.40 0.61 曲而 曲而 0.65 4萬張 0.42 0.33 0.35 0.41 0.70 無法 無法 0.61 6萬張 0.34 0.44 0.43 0.38 0.77 評量 評量 0.79 8萬張 0.37 0.41 0.40 0.40 0.83 0.88 10萬張 0.32 0.39 0.44 0.39 1.04 1.13 偏位 初期 A A A A A C C A 及捲 2萬張 A A A A A 一 一 A 曲性 4萬張 A A A A A 一 一 A 31 1248564 6萬張 A A A A A 一 — A 8萬張 A A A A A — 一 A 10萬張 A A A B A 一 — A 分 散 初期 一 — — — — 因 捲 因 捲 — 2萬張 0.1 2 0.1 5 0.1 1 0.1 3 0.22 曲 而 曲 而 0.26 4萬張 0.1 4 0.1 9 0.16 0.13 0.32 ΓΠΤΤ J\\\ 法 法 0.35 6萬張 0.1 7 0.1 9 0.16 0.15 0.38 評 量 評 量 0.40 8萬張 0.1 7 0.22 0.15 0.16 0.44 0.48 10萬張 0.1 8 0.23 0.17 0.19 0.49 0.52 消 耗 初期 — — — 一 — 因 捲 因 捲 — 1 1 2萬張 23.1 24. 2 23.7 22.2 28. 5 曲 而 曲 而 29.5 4萬張 23. 6 23. 8 23.2 23.5 28. 8 J\ \\ 法 >fnT· Μ 法 28.2 6萬張 23. 4 23. 5 23.1 23.2 27. 7 評 量 評 里 29.8 8萬張 24.1 23.1 23.6 23.9 29. 4 27.4 10萬張 24. 3 24.1 23.9 24.1 29. 8 26.8 轉 印 初期 — — — 一 — 因 捲 因 捲 —— 效 率 2萬張 93. 2 92.1 92.6 89.2 84.1 曲 而 曲 而 85.1 4萬張 91 . 9 91 . 3 90.1 90.1 85. 9 >fnr Μ1II y \ \\ 法 >fnrr ΤΠΤΤ 法 84.3 6萬張 90. 4 92. 4 88.2 88.6 82. 4 評 量 評 量 81.6 8萬張 91 . 2 90. 5 89.9 89.4 80.1 79.1 10萬張 90. 6 89. 7 90.2 90.3 78. 5 77.5 ”COC :環烯烴共聚物樹脂、PES :聚酯樹脂 32 1248564 在實施例4至7 '比較例1中’目視芳 確認不會隨著多枚連續印刷而劣化。 在比較例2至4中，目視定像輥表面琅 印紙的位置上會因摩擦而劣化。 <評量結果〉 由表1可明白：在實施例4至7中，從 萬張後之影像濃度爲1.40以上，白度差在 用上可以無問題地複印，而且沒有偏位及捲 之BS、向顯像材料之熔融黏著，可確認帶電 耐久性亦沒問題。在比較例1及4中，推測 爲影像濃度降低之原因，且可確認具有白度 種問題。又，使用環烯烴共聚物樹脂的調色 樹脂之調色劑比起來，也可確認顯示出較佳 印效率。 更且，在比較例2和3中，在初期即引 曲，以致無法繼續進行評量。比較例4、比車 多是同樣的結果，因而不能辨認P B I對聚酯 效果。 依照上述評量結果，可以確認P B丨對於 樹脂而言具有效性。 【圖式之簡單說明】 第1圖係在定像組件爲輥的情況下使用 熱壓著式定像機之模式圖。 像輥表面時， ，確認通過轉 初期開始到1 〇 0.44以下，實 曲、向感光體 性、定像性及 向載體分散係 差增加等之種 劑與使用聚酯 的消耗量及轉 起定像輥之捲 交例1也差不 之於定像輥的 環烯烴共聚物 於本發明之加 33 1248564 第2圖係在定像組件爲輥的情況下使用於本發明之加 熱壓著式定像機之模式圖。 【元件符號對照表】 1 定像輥 2 含P BI表層 3 鋁製芯管 4 熱源 5 加壓輥 6 轉印紙 7 調色劑影像 8 由PBI形成的薄膜之帶 34EXAMPLES Examples Examples Comparative Examples Comparative Examples Comparative Examples 4 5 6 7 1 2 3 4 Adhesive COC COC COC COC PES COC COC PES Toner ABCADACD Fixing Roller PBI PBI PBI PBI/ PBI PTFE PTFE PTFE醯imino ID Initial 1.48 1.53 1.41 1 .45 1.42 Due to the volume of 1.44 20,000 sheets 1.47 1.55 1.42 1 .46 1.40 曲曲曲 1.44 4 thousand sheets 1.47 1.53 1.40 1.46 1.42 Cannot be unable to 146,600 sheets 1.46 1.52 1.42 1.47 1.35 Evaluation and assessment 1.36 million sheets 1.48 1.54 1 .42 1.45 1.31 1.34 100,000 sheets 1 . 47 1 .55 1 .41 1 .45 1.25 1 .27 BG Initial 0.33 0.38 0.41 0.38 0.52 Due to the volume of 0.59 20,000 sheets 0.35 0.37 0.38 0.40 0.61 曲曲曲0.65 4,000 sheets 0.42 0.33 0.35 0.41 0.70 Can not be 0.61 60,000 sheets 0.34 0.44 0.43 0.38 0.77 Evaluation and evaluation 0.79 80,000 0.37 0.41 0.40 0.40 0.83 0.88 100,000 sheets 0.32 0.39 0.44 0.39 1.04 1.13 AAAAACCA and 20,000 AAAAA in the initial stage of partiality A-A 40,000 AAAAA One A1 12 1248564 60,000 AAAAA one — A 80,000 AAAAA — one A 100,000 AAABA one — A initial dispersion — one — because of the volume of the volume — 20,000 sheets of 0.1 2 0.1 5 0.1 1 0.1 3 0.22 and the number of 0.26 4 thousand sheets 0.1 4 0.1 9 0.16 0.13 0.32 ΓΠΤΤ J\\\ Method 0.35 60,000 sheets 0.1 7 0.1 9 0.16 0.15 0.38 Evaluation of 0.40 80,000 sheets 0.1 7 0.22 0.15 0.16 0.44 0.48 100,000 sheets 0.1 8 0.23 0.17 0.19 0.49 0.52 — — — 一 — Because of the volume of the volume — 1 1 2 2 sheets 23.1 24. 2 23.7 22.2 28. 5 曲曲曲29.5 4万张 23. 6 23. 8 23.2 23.5 28. 8 J\ \\ Method> fnT· Μ method 28.2 6 2, 23. 4 23. 5 23.1 23.2 27. 7 Evaluation of 29.8 8 million 24.1 23.1 23.6 23.9 29. 4 27.4 100,000 sheets 24. 3 24.1 23.9 24.1 29. 8 26.8 Transfer In the early days — — — — — — — — — — — — — — — — — — — — — — — — — — — — Method > fnrr ΤΠΤΤ method 84.3 6 million 90. 4 92. 4 88.2 88.6 82. 4 Evaluation of 81.6 8 million 91 . 2 90. 5 89.9 89.4 80.1 79.1 100,000 sheets 90. 6 89. 7 90.2 90.3 78. 5 77.5 ”COC: cycloolefin copolymer resin, PES: polyester resin 32 1248564 In Examples 4 to 7 'Comparative Example 1', visual confirmation was not deteriorated with a plurality of continuous printings. In Comparative Examples 2 to 4, the position of the fixing roller surface on the surface of the printing paper was deteriorated by friction. <Evaluation result> It can be understood from Table 1 that in Examples 4 to 7, the image density after 10,000 sheets is 1.40 or more, and the whiteness difference can be copied without problems, and there is no offset and volume. The BS and the fusion bonding to the developing material can confirm that the charging durability is not problematic. In Comparative Examples 1 and 4, it was presumed that the image density was lowered, and it was confirmed that there was a problem of whiteness. Further, it was confirmed that the toner of the toner of the cycloolefin copolymer resin was used to exhibit a better printing efficiency. Further, in Comparative Examples 2 and 3, the introduction was made at an early stage, so that the evaluation could not be continued. In Comparative Example 4, the same result was obtained as compared with the vehicle, and thus the effect of P B I on the polyester could not be recognized. According to the above evaluation results, it was confirmed that P B 具 is effective for the resin. [Simple description of the drawing] Fig. 1 is a schematic view showing the use of a thermocompression type fixing machine in the case where the fixing unit is a roller. When it is like the surface of the roll, it is confirmed that the amount of the agent and the amount of the polyester used and the amount of the polyester used in the initial stage of the rotation are less than 1 〇 0.44 or less, and the amount of the agent, the photoreceptor, the fixing property, and the dispersion to the carrier are increased. The roll-to-olefin copolymer of Example 1 is also inferior to the cycloolefin copolymer of the fixing roller. In the case of the present invention, 33 1248564. FIG. 2 is used in the case of the fixing assembly as a roller, and is used in the heating and pressing type of the present invention. The mode diagram of the camera. [Component Symbol Comparison Table] 1 Fixing Roller 2 P P surface layer 3 Aluminum core tube 4 Heat source 5 Pressurizing roller 6 Transfer paper 7 Toner image 8 Film strip formed by PBI 34